Method for preparing isoindolenone pigments

ABSTRACT

A method of preparing an isoindolenone pigment represented by the general formula   WHEREIN X is a halogen atom, n is 0 or an integer of 1 - 4, and R is a direct bond, divalent aromatic residue or divalent heterocyclic residue, WHEREIN A COMPOUND REPRESENTED BY THE GENERAL FORMULA   WHEREIN X, n and R are as defined above, is subjected to intramolecular dehydrocondensation.

United States Patent Ando et al. Dec. 2, 1975 METHOD FOR PREPARING ISOINDOLENONE PIGMENTS [75] Inventors: Hirohito Ando, Urawa; Kunihiko Takagi, Tokyo, both of Japan 73] Assignee: Dainippon Ink & Chemicals, n16, NH HN Tokyo, Japan 22 Filed: Apr. 25, 1973 Xn M 21 Appl. N0.: 354,194 0 wherein X is a halogen atom, n is O or an integer of l 4 52 us. Cl 260/152;260/295 K; 260/165; g i g fiz 2 2?; i f

260/305; 260/325; 260/558 P; 106/288 0 s n m y 51 Im. 01. ..C07D 209 50; C09B 57 00; wherein a compound represented by the general for C07C 103/76 mula [58] Field of Search 260/305, 325 PH, 295 K,

260/1, 165, 152 CONH R HNOC [56] References Cited UNITED STATES PATENTS 3,496,190 2/1970 Von der Crone 260/325 Xn CON'H H NOC xn Primary ExaminerDonald G. Daus Assistant Examiner-Diana G. Rivers Attorney, Agent, or Firm-Sherman & Shalloway [57] ABSTRACT A method of preparing an isoindolenone pigment represented by the general formula TRAI;JSMISSION SZOEFFICIENT ("/o) o 0 00 WAVE NUMBER km") are as defined above, is intramolecular wherein X, n and R subjected to dehydrocondensation.

8 Claims, 1 Drawing Figure US. Patent Dec. 2, 1975 OO m CON.

A v KmmSBZ m 00 2 dium, and the reaction (2) allows rapid condensation METHOD FOR PREPARING ISOINDOLENONE reaction making it hard to control the reaction.

PIG M ENTS This invention relates to a method for preparing 5 isoindolenone pigments.

Conventional methods for preparing isoindolenone pigments include a method (Swiss Pat. Nos. 346,218, 348,496 and 363,980) in which an isoindoline having three or more halogen atoms on the aromatic nucleus is The object of this invention, therefore, is to overcome such drawbacks inherent in the conventional methods and to provide a new method which allows easy progressing of the reaction contributing to the formation of isoindolenone pigments in high yield and high purity and cheaply as well.

reacted with a poly-primary amino compound, being Other objects of this invention will become clear as represented, for example, by the reaction formulas; the description proceeds.

Cl //NH C C.@ 2 NH H N -NH CZ C H C2 0 (2) c2 c1 c1 H CO C Cl 2 NH H N -1\1H cz c in order to obtain the pigments of the formula; The inventors of this application have found that by heating the compounds represented by the general formula c1 cl e CONH R HNOC I (I) /NH X/" at com! H NOC 1 g I n 2 2 n Ci 0 Cfl in which X is a halogen atom, n is O or an integer of I 1-4, d R d'rect bond, d alent a omatic sand a method (US. Pat. No. 2,537,352) in which an re 1 due or divalent hetercoychc residue,

hav'mg 9 substlmeit or together with phosphorus pentachloride or phosphorus substltuents on the aromatic nucleus 18 reacted with a pentabmmide as a condensing agent (dehydrating divalent aromatic dlamme. Practical operation based agent) in an inert organic Solvent for the purpose of on these methods, however, involves rn y Problems ausing intramolecular dehydrocondensation, the For example, preparation of isomdolme-l-one faces isoindolenone pigments of the general formula many limitations; halophthalimides or o-cyano benzoic acid esters which serve as raw materials are not easily N R N available, and where a halophthalimide is used as a raw 6 C C material, an intermediate of high purity is difficult to 6 obtain in a high yield. Furthermore, when conducting the reaction of isoindoline-l-one with diamine, the C C abovementioned reactions l) and (3) require the use X g g of troublesome glacial acetic acid as a reaction me- 3 in which X, n R are as defined above, are obtained in high yields and high purity, thereby'satisfying the above-mentioned object'of this invention.

As the inert organic solvent mentioned above, there may be used preferably benzene, I toluene, xylene, monochlorobenzene, o-dichlorobe'nzene, trichlorobenzene, dichloroethane, trichloroethane, tetrachloroethane, nitrobenzene, decalin, diphenyl ether, etc. The amount of the condensing agent should be more than 2 mole ratio, and preferably 3 4 mole ratio. The heating requires a temperature of above 60C. But a temperature exceeding 130C is not desired as the product gets foul and reduces the value of pigment. Optimal heating temperature ranges 70 to 80C. The reaction completes in about 0.5 to 4 hours, being very simple, and imposes no problem for industrialization.

The compound of the formula (I) used as a raw material for making isoindolenone pigments of this invention can be obtained very easily by condensing a phthalic anhydride or a halophthalic anhydride having 1 4 halogen atoms on the aromatic nucleus, with hydrazine, an aromatic diamine, or a heterocyclic diamine, in an inert organic solvent by using a condensing agent such as phosphorus pentachloride, phosphorus trichloride, thionyl chloride, acetyl chloride, phosphorus oxybromide, or acetyl bromide, and then adding ammonia water to the reaction mixture or directly blowing ammonia gas to the reaction mixture. As inert organic solvents, those used for causing intramolecular dehydrocondensation reaction can be used preferably.

As examples of the halophthalic anhydride having 1 4 halogen atoms on the aromatic nucleus which is used as one of the raw materials for making the compound of the formula (I), there may be cited 3-chlorophthalic anhydride, 4-chlorophthalic anhydride, 3,4- dichlorophthalic anhydride, 3,5-dichlorophthalic anhydride, 3,6-dichlorophthalic anhydride, 4,5-dichlorophthalic anhydride, 3,4,5-trichlorophthalic anhydride, 3,4,6-trichlorophthalic anhydride, 3,4,5,6-tetrachlorophthalic anhydirde, 3-bromophthalic anhydride, 4-bromophthalic anhydride, 3,4-dibromophthalic anhydride, 3,5-dibromophthalic anhydride, 3,6- dibromophthalic anhydride, 4,5-dibromophthalic anhydride, 3,4,5-tribromophthalic anhydride, 3,4,6-tribromophthalic anhydride, 3,4,5,6-tetrabromophthalic anhydride, 3-fluorophthalic anhydride, 4-fluorophthalic anhydride, 3,4-diflurophthalic anhydride, 3,5- difluorophthalic anhydride, 3,6-difluorophthalic anhydride, 4,5-difluorophthalic anhydride, 3,4,5-trifluorophthalic anhydride, 3,4,6-trifluoropht'halic anhydride, and 3,4,5,-tetrafluorophthalic anhydride.

As the aromatic diamine or heterocyclic diamine used as another raw material for making the compound of the formula (I), diamines used so far as a raw material for making isoindolenone pigments can be used. As examples of such diamines, there may be cited o-, m-, p-phenylenediamines, benzidine, o-dianisidine, o-, mtolidines, 3,3'-dichlorobenzidine, 4,4'-diaminodiphe- The process of preparing the compounds of the formula (I) is exemplified below as Reference Example.

4 I REFERENCE EXAMPLE:

54 Grams'of'p-phenylenediamine was dissolved in 900 ml of dimethylformamide with stirring at room temperature, and to the so obtained solution was added 300 g of tetrachlorophthalic anhydride maintaining a temperature below 30C. The resulting solution was then stirred for one hour and was admixed with 44 ml of phosphorus trichloride dropwise. The mixture was then stirred at the same temperature for 2 hours. By siowly adding 180.5 ml of 28% by weight of ammonia water to the reaction mixture in which has been suspended a precipitated condensate, and stirring the mixture at 30C for 4 hours, a white crystalline substance was precipitated. The mixture was poured into 1 liter of ice water and was filtered. The white residue was again suspended in 2 l of water and was stirred for one hour at 90C, followed by hot filtration, and then dried sufficiently. The yield was 329 g. The drawing' attached shows the infrared ray absorption spectrum of the product. From the drawing, it was confirmed that the product is a compound which can be represented by the structural formula Ci Ci CONH- -HNOC or 1/ i Ci CONH H NOC Ci Cl CZ The invention is illustrated below with reference to Examples, and parts are all by weight unless otherwise specified.

EXAMPLE 1:

l3.6 Parts of the compound represented by the structural formula cz oz CONH- -NHOC cz or I Ci CONH2 HZNOC Cl 01 c2 and 12.5 parts of phosphorus pentachloride were stirred in 100 parts of trichlorobenzene at a temperature of C for 3 hours, cooled and filtered. The residue was washed sufficiently with methanol and then with water, and dried. 10.? Parts of a reddish yellow compound was obtained. By comparing the so obtained. compound with the known compound by means of in-. frared ray absorption spectrum, it was confirmed that the compound is a pigment represented by the structural formula A paint prepared by kneading the so obtained pigment together with a melamine alkyd resin was sprayed on a tin plate and baked at a temperature of 120C. For bleed testing, a titanium white/melamine alkyd paint was sprayed onto the coated surfaces of a tin plate, and baked at temperatures of 140C and 160C. In both cases, no bleeding occurred.

Also, a paint prepared by kneading the pigment and melamine alkyd resin together with titanium white in an amount ten times that of the pigment, was sprayed onto the tin plate and baked at a temperature of 120C. The sample was tested for weatherability, and a very good result was obtained.

EXAMPLEYZ:

15.0 Parts of the compound represented by the structural formula proved that the compound so obtained is a pigment which can be represented by the structural formula Cl N 011 of 1 1 NH c2 (3 or o 2 By kneading the pigment with vinyl chloride resin by means of a heated roll, a clear orange vinyl chloride resin sheet was obtained. The pigment showed itself to be very good in heat resistance, migration resistance, and whetherability.

EXAMPLE 3:

Process of Example 1 was repeated by using 13.9 parts of the compound represented by the structural formula Ci NHOC and 11.2 parts of a bluish yellow compound was obtained. -Comp'arison with the known compound by me'ans of'infrared ray absorption spectrum proved that the compound is a pigment which can be represented by the structural formula N Q o NH l-EN EXAMPLE 4;

15.6 Parts of the compound represented by the structural formula H CO and 12.5 parts of phosphorus pentachloride were heated at 70 -80C and stirred for 3 hours in 150 parts of toluene. After cooling, the mixture was admixed 40 with 10 parts of pyridine, and filtered, and then washed sufficiently with toluene, methanol, and hot water in the order mentioned, and dried. 102 Parts of a reddish compound was obtained. Comparison with the known compound by means of infrared ray absorption spectrum has proved the compound so obtained to be a pigment which can be represented by the structural formula Examples 1 4 and melamine alkyd resin together with titanium white in an amount 20 times that of the pigment were coated on the tin plates, and exposed outdoors fortwo years. Results were as shown in Table 1 below.

Table 1 Example 1 Example 2 Example 3 Example 4 Color tone of reddish bluish pigment yellow orange yellow red Color difference 0.92 2.l2 3.45 4.82 (AE) EXAMPLE 5; EXAMPLE 7:

8.0 Parts of the compound represented by the structural formula CONT-l H NOC and 8.4 parts of phosphorus pentachloride were heated at 60C and stirred for one hour in 80 parts of trichlorobenzene, and blown with ammonia gas, neutralized, cooled, and filtered. The residue was washed sufficiently with ethanol and then water, and dried. A clear yellow compound was obtained. The infrared ray absorption spectrum has proved the compound to be a pigment represented by the structural formula EXAMPLE 6:

13.6 Parts of the compound represented by the structural formula i NH C ll Cl 0 2 10.8 Parts of the compound represented by the structural formula CZ HZNOC/ CONH and 34.4 parts of phosphorus pentabromide were stirred at 120C for 30 minute in 100 parts of dichloroethane, neutralized with ammonia gas, cooled and filtered. The residue was washed with methanol and then with hot water. A bluish yellow compound was obtained. The infrared ray absorption spectrum has proved the compound to be a pigment of the structural formula 20.7 Parts of the compound represented by the structural formula 131' Br l CONH- 'HNOC I Br m Br I Br coma HZNOC 1 Br Br and 12.5 parts of phosphorus pentachloride were stirred at C for 4 hours in parts of trichlorobenzene, added with 10 parts of anhydrous sodium acetate, and filtered maintaining a temperature of 50- 60C. The residue was washed sufficiently with methanol and then with hot water, and dried. A clear yellowish compound was obtained. The infrared ray absorption spectrum has proved the compound to be a pigment of the structural formula 7 EXAMPLE 9:

13.0 Parts of the compound represented by the structural formula H C F 3 l CONH\ 2 F 10 l EXAMPLE 10; F CONH A variety of compounds represented by the formula 2 (I) were used as starting materials and treated in the F 2 same manner as in the above-mentioned Examples to obtain a variety of isoindolenones. lnTable 2, below, col. 1 shows I CO and 12.5 parts of phosphorus pentachloride were stirred at 100C for 1.5 hours in 150 parts of xylene, CONH cooled and filtered. Then the residue was washed suffi- 2 ciently with xylene, methanol, and hot water in the Xn order mentioned. A yellowish compound was obtained. The infrared ray absorption spectrum has proved the comp n nt of f rm la (l), L 2 shows -N- compound to be a pigment which can be represented HRl-lN-- component of formula (I), and col. 3 by the structural formula shows the color tone of the pigment obtained.

Table 2 Component of formula (1) Color tone of pigment coobtained NHR-HN- coNH 5:111:11 Cl co NH HN- ..NH--gH -HN bluish yellow H -NH yellow reddish ellow -NH-' NHC o Q- y Table 2-continued Component of formula (1) Color l I tone pigment co obtained NHRHN CONH . C I l, NHQ HN yellow .Cl

yellowish NH N N orange 1 coNH H orange bluish yellow NH yellow c -H N- C 1 CO reddish N H HN yellow 1 CONH2 -NH HN reddish c1 CONHZ yellow .co "3 0 OCH 3 1 Bl CO- 3 Br coml @-HN- red What is claimed is: 1. A method of preparing an isoindolenone pigment of the formula N-R-N\ NH HN c c Xn H H Km 0 CONH-R-HNOC CONH H NOC Xn Xn wherein X, n, and R are as defined above, at a temperature of from 60 to 130C. and in the presence of both an inert organic solvent and at least 2 mols per mol of the above compound of a condensing agent.

2. A method according to claim 1, wherein the heating is performed at a temperature ranging to C.

3. A method according to claim 1, wherein benzene, toluene, xylene, chlorobenzenes, chloroethanes, nitrobenzene, decalin, or diphenylether isused as the inert organic solvent.

4. A method according to claim 1 wherein the condensing agent is present in from 3 to 4 mols per mol of the compound. v

5. A method according to claim 1 wherein the condensation reaction takes from 0.5 to 4 hours.

'6. A method according to claim 1 wherein the condensing agent is phosphorous pentachloride or phosphorous pentabromide.

7. A method according to claim 1 wherein X is chlorine or bromine.

8. A method according to claim 1 wherein R is the residue of one of the group comprising p-phenylenediamine, 2,6-diaminotoluene, benzidine, 2,2- diaminodiphenyl, o-dianisidine, or diaminoazoben- It is; certified that error zmpeurs in the above-identified pate-:11 and that said Letters Patent are hereby corrected as shown below:

Item 54, line 2, delete "ISOINDOLENONE", insert ISOINDOLINONE Column 10, line 16, delete "isoindolenones", insert isoindolinones r Delete "isoindolenone" and insert isoindolinone in the following instances:

Item 57, line 2;

3 Claim 1, line 1.

Signed and Scaled thisthirtieth D f March 1976 [SEAL] A ties t:

RUTH C. MASON Arresting Officer C. MARSHALL DANN u m m issionvr nfPaIents and Trademarks Patent H g glgijg December, Z v l9l5..W..-

'.[nventor(s-;) ANDO, ET Al It is; certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below-x:

Item 54, line 2, delete "ISOINDOLENONE", insert ISOINDOLINONE Column 10, line 16, delete "isoindolenones", insert isoindolinones Delete "isoindolenone" and insert isoindolinone in the following instances Item 57, line 2;

Claim 1,. line 1.

n'gncd and Scaled thisthirtieth D ay 0f March I 9 76 [SEAL] A ttest:

RUTH C. M AHSON C. MARSHALL DANN Arresting Officer Commissioner oj'latems and Trademarks 

1. A METHOD OF PREPARING AN ISOINDOLENONE PIGMENT OF THE FORMULA ((1-(O=),(X)N-ISOINDOLIN-3-YLIDENE)=N-)2-R WHEREIN X IS A HALOGEN ATOM, N IS A NUMBER FROM 0 TO 4, AND R IS A DIRECT BOND, OR DIVALENT RESIDUE OF ONE OF THE GROUP CONSISTING OF O-, M-, P-PHENYLENEDIAMINES, BENZIDINE, ODIANISIDINE, O-, M-TOLIDINES, 3,3''-DICHLOROBENZIDINE, 4,4''DIAMINODIPHENYL METHANE, 3,3''-DICHLORO-4,4''DIAMINODIPHENYL METHANE, 4,4''-DIAMINODIPHENYL ETHER, 1,5-DIAMINONAPHTHALENE, 2,2''-DIAMINODIPHENYL, 2,6DIAMINOTOLUENE, 2,6-DIAMINOPYRIDINE, 2,6-DIAMINOBENZOTHIAZOLE, DIAMINOAZOBENZENE, N-(P''-AMINOPHENYL)PAMINOBENZAMIDE, OR 2,2''-DICHLOROBENZIDENE; COMPRISING THE STEP OF CONDENSING A COMPOUND OF THE FORMULA ((2-(H2N-CO-),(X)N-PHENYL)-CO-NH-)2-R WHEREIN X, N, AND R ARE AS DEFINED ABOVE, AT A TEMPERATURE OF FROM 60* TO 130*C. AND IN THE PRESENCE OF BOTH AN INERT ORGANIC SOLVENT AND AT LEAST 2 MOLS PER MOL OF THE ABOVE COMPOUND OF A CONDENSING AGENT.
 2. A method according to claim 1, wherein the heating is performed at a temperature ranging 70* to 80*C.
 3. A method according to claim 1, wherein benzene, toluene, xylene, chlorobenzenes, chloroethanes, nitrobenzene, decalin, or diphenylether is used as the inert organic solvent.
 4. A method according to claim 1 wherein the condensing agent is present in from 3 to 4 mols per mol of the compound.
 5. A method according to claim 1 wherein the condensation reaction takes from 0.5 to 4 hours.
 6. A method according to claim 1 wherein the condensing agent is phosphorous pentachloride or phosphorous pentabromide.
 7. A method according to claim 1 wherein X is chlorine or bromine.
 8. A method according to claim 1 wherein R is the residue of one of the group comprising p-phenylenediamine, 2,6-diaminotoluene, benzidine, 2,2''-diaminodiphenyl, o-dianisidine, or diaminoazobenzene. 